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Item Ambient ionization mass spectrometric analysis of human surgical specimens to distinguish renal cell carcinoma from healthy renal tissue(Springer, 2016-08) Alfaro, Clint M.; Jarmusch, Alan K.; Pirro, Valentina; Kerian, Kevin S.; Masterson, Timothy A.; Cheng, Liang; Cooks, R. Graham; Urology, School of MedicineTouch spray - mass spectrometry (TS-MS) is an ambient ionization technique (ionization of unprocessed samples in the open air) that may find intraoperative applications in quickly identifying the disease state of cancerous tissues and in defining surgical margins. In this study, TS-MS was performed on fresh kidney tissue (~1–5 cm3), within one hour of resection, from 21 human subjects afflicted by renal cell carcinoma (RCC). The preliminary diagnostic value of TS-MS data taken from freshly resected tissue was evaluated. Principal component analysis (PCA) of the negative ion mode (m/z 700–1000) data provided separation between RCC (16 samples) and healthy renal tissue (13 samples). Linear discriminant analysis (LDA) on the PCA compressed data estimated sensitivity (true positive rate) and specificity (true negative rate) of 98% and 95%, respectively, based on histopathological evaluation. The results indicate that TS-MS might provide rapid diagnostic information in spite of the complexity of unprocessed kidney tissue and the presence of interferences such as urine and blood. Desorption electrospray ionization imaging (DESI-MSI) in the negative ionization mode was performed on the tissue specimens after TS-MS analysis as a reference method. The DESI imaging experiments provided phospholipid profiles (m/z 700–1000) that also separated RCC and healthy tissue in the PCA space, with PCA-LDA sensitivity and specificity of 100% and 89%, respectively. The TS and DESI loading plots indicated that different ions contributed most to the separation of RCC from healthy renal tissue (m/z 794 [PC 34:1+Cl]− and 844 [PC 38:4+Cl]− for TS vs. m/z 788 [PS 36:1-H]− and 810 [PS 38:4-H]− for DESI), while m/z 885 ([PI 38:4-H]−) was important in both TS and DESI. The prospect, remaining hurdles, and future work required for translating TS-MS into a method of intraoperative tissue diagnosis is discussed.,Item Detection and Quantitation of Hazardous Chemicals in Environmental Matrices using Paper Spray Mass Spectrometry(2019-08) Dowling, Sarah Naciye; Manicke, Nicholas; Goodpaster, John; Sardar, RajeshPaper spray mass spectrometry (PS-MS) is an ambient ionization technique that has been proven useful in many types of investigative analyses. However, the use of this technique with regards to environmental samples has been largely unexplored since the technique’s development. In this work, paper spray mass spectrometry was utilized to detect and quantify compounds for environmental, forensic and chemical defense applications. Due to the sensitive nature of some projects, the work was split into two volumes. Volume 1 focuses on the detection of pharmaceuticals in soil using paper spray (Chapter 2) and the detection of chemical warfare agent (CWA) simulants and CWA hydrolysis products (Chapter 3). Volume 2 focuses on the detection and quantitation of fentanyl analogs in environmental matrices. Chapter 5 focuses on the rapid analysis of fentanyl analogs in soil matrices. The following chapter evaluates the ability of PS-MS to detect low concentrations of fentanyl analogs in water (Chapter 6). Throughout this work, paper spray has proven to be an effective, rapid alternative to chromatography for the analysis of environmental samples.